US5274060A - Copolymers crosslinkable by acid catalysis - Google Patents
Copolymers crosslinkable by acid catalysis Download PDFInfo
- Publication number
- US5274060A US5274060A US07/843,798 US84379892A US5274060A US 5274060 A US5274060 A US 5274060A US 84379892 A US84379892 A US 84379892A US 5274060 A US5274060 A US 5274060A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- hydrogen
- phenyl
- acid
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 37
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000002367 halogens Chemical group 0.000 claims abstract description 17
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- 125000006239 protecting group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 4
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims abstract description 3
- -1 ethylene, propylene Chemical group 0.000 claims description 30
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 claims 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 claims 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 33
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 7
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 29
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- GOVKKMYVXPXUOS-UHFFFAOYSA-N 2-(4-ethenylphenyl)-1,3-dioxolane Chemical compound C1=CC(C=C)=CC=C1C1OCCO1 GOVKKMYVXPXUOS-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- OODGPKJPJBOZQL-UHFFFAOYSA-N 2-(4-ethenylphenoxy)oxane Chemical compound C1=CC(C=C)=CC=C1OC1OCCCC1 OODGPKJPJBOZQL-UHFFFAOYSA-N 0.000 description 5
- QBFNGLBSVFKILI-UHFFFAOYSA-N 4-ethenylbenzaldehyde Chemical compound C=CC1=CC=C(C=O)C=C1 QBFNGLBSVFKILI-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- HXUPBTARAJNKAJ-UHFFFAOYSA-N 1-(dipropoxymethyl)-4-ethenylbenzene Chemical compound CCCOC(OCCC)C1=CC=C(C=C)C=C1 HXUPBTARAJNKAJ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017048 AsF6 Inorganic materials 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910016858 F5 SO3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-methyl-PhOH Natural products CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000001393 microlithography Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- QDSBRLMOWFYBGK-UHFFFAOYSA-N phenacyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC(=O)C1=CC=CC=C1 QDSBRLMOWFYBGK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000005537 sulfoxonium group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPBNICVODIHXKB-UHFFFAOYSA-N tert-butyl 4-ethenylbenzoate Chemical compound CC(C)(C)OC(=O)C1=CC=C(C=C)C=C1 HPBNICVODIHXKB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- CVJLQNNJZBCTLI-UHFFFAOYSA-M triphenylsulfanium;iodide Chemical compound [I-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 CVJLQNNJZBCTLI-UHFFFAOYSA-M 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- the present invention relates to copolymers of acetalised and OH-group-containing vinylbenzenes or N-phenylmaleimides that are crosslinkable by acid catalysis, to photosensitive compositions comprising such copolymers and an acid-forming substance, and to the use thereof as negative resists for the production of protective coatings and relief structures.
- Negative resist compositions that work according to the so-called chemical amplification principle are known from the literature.
- J. M. F. Frechet et al. describe in Polym. Mat. Sci. Eng., 60 (1989) 147-150, in Macromolecules, 24 (1991) 1746-1754 or in Polymer Engineering and Science, 29 No. 14 (July 1989) 960-964 negative resists of the amplification type based on electrophilic aromatic substitution.
- copolymers are produced from 4-tert-butoxycarbonylstyrene and 4-acetoxymethylstyrene and, after removal of the tert-butoxycarbonyl protecting groups, those copolymers are irradiated with UV light at 254 nm in the presence of a triarylsulfonium salt as acid generator, such as triphenylsulfonium hexafluoroantimonate, the irradiated areas becoming crosslinked.
- a triarylsulfonium salt as acid generator such as triphenylsulfonium hexafluoroantimonate
- 3-component systems consisting of polyfunctional low-molecular-weight latent electrophiles, such as 1,4-bis(acetoxymethyl)benzene, a triarylsulfonium salt and a phenolic polymer.
- polyfunctional low-molecular-weight latent electrophiles such as 1,4-bis(acetoxymethyl)benzene, a triarylsulfonium salt and a phenolic polymer.
- Similar negative resist systems based on onium salts a polyfunctional compound having activated aromatic rings and a polyfunctional compound supplying carbonium ions, at least one of those two compounds being a polymer or copolymer, are described in U.S. Pat. No. 4,800,152.
- M Hatzakis et al. describe in Microelectronic Engineering, 11 (1990) 487-490 negative resist compositions based on epoxidised novolaks and onium salts as acid-generating substances. These latter systems cannot be developed in an aqueous-alkaline
- the invention relates, therefore, to copolymers having a molecular weight (Mw) of from 10 3 to 10 6 , measured by gel-permeation chromatography, that are crosslinkable by acid catalysis and that consist of
- R is hydrogen or a protecting group that can be removed by the action of acids
- the radicals R 2 each independently of the other are hydrogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy
- R 5 and R 7 are each hydrogen
- R 6 is hydrogen, halogen or methyl
- R 8 is hydrogen, halogen, methyl, --CH 2 halogen, --CH 2 CN, --CN, --COOH, --CONH 2 , --O--C 1 -C 5 alkyl, --O-
- the copolymers according to the invention preferably have a molecular weight (Mw) of from 5000 to 500,000, especially from 5000 to 20,000.
- X and X' are preferably ##STR7## and, especially, are each ##STR8##
- protecting groups R that can be removed by the action of acids are radicals of formulae IV to VII ##STR9## --COO--C(CH 3 ) 3 (VI) and --CO--R 13 (VII), wherein R 9 is hydrogen or methyl, R 10 is C 1 -C 5 alkyl, phenyl or naphthyl and R 11 and R 12 each independently of the other are hydrogen, C 1 -C 5 alkyl, phenyl or naphthyl, or R 10 and R 12 together are ethylene, propylene or butylene each unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, naphthyl, phenoxy or by naphthyloxy, y is 2, 3 or 4, and R 13 is C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
- Alkyl groups represented by R 1 , R 2 , R 10 , R 11 , R 12 or R 13 or present in radicals R 8 , R 10 and R 12 , and alkoxy groups R 2 and R 13 or alkoxy groups present in radicals R 10 or R 12 may be straight-chained or branched. Examples that may be mentioned are: methyl, ethyl, n-propyl, isopropyl, n-, sec- and tert-butyl, n-pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n- and tert-butoxy and n-pentyloxy.
- R 1 , R 2 , R 10 , R 11 and R 12 as alkyl or alkoxy are especially methyl, ethyl, methoxy or ethoxy, more especially methyl or methoxy.
- Halogen in groups R 6 and R 8 is e.g. Cl, Br or F.
- the two radicals R 1 are preferably --[C(R 3 )(R 4 )] x -- wherein x is from 2 to 4, especially 2 or 3.
- the radicals R 2 are preferably hydrogen.
- R 9 has the meaning given above, R 10 is methyl or ethyl, R 11 and R 12 each independently of the other are hydrogen or methyl, or R 10 and R 12 together are unsubstituted ethylene or propylene.
- y in radicals of formula V is preferably 2 or 3
- R 13 is especially C 1 -C 5 alkoxy, more especially tert-butoxy.
- R is preferably hydrogen or --COO--C(CH 3 ) 3 and is especially a radical of formula V wherein y is 2 and especially 3. Most preferably, R is hydrogen.
- copolymers according to the invention can be prepared in a manner known per se by radical copolymerisation of 100-80 mol. % of compounds of formulae Ia and IIa ##STR10## in a ratio of from 1:1 to 1:9 and 0-20 mol. % of a compound of formula IIIa ##STR11## wherein R, R 1 , R 2 and R 5 to R 8 are as defined above and X" is ##STR12## and, if desired, acid-catalysed removal of the protecting group R.
- the radical copolymerisation can be carried out using various techniques. These have been described, for example, by S. Sandler and W. Karo in "Polymer Synthesis", vol. 1-3, 1968, Academic Press, New York. Customary polymerisation methods are, for example, mass polymerisation, solvent polymerisation, emulsion polymerisation, suspension polymerisation or precipitation polymerisation.
- the starting materials of formula Ia are known or can be prepared according to methods known per se, for example by reaction of the corresponding benzaldehydes with pyrocatechol, mono- or di-hydroxy compounds R 1 OH or HO--[C(R 3 )(R 4 )] x --OH.
- the compounds of formula IIIa are also known and some of them are available commercially.
- monomers of formula IIIa are ethylene, propylene, styrene, ⁇ -methylstyrene, acrylonitrile, ⁇ , ⁇ -unsaturated acids and amides, such as, for example, acrylic acid, acrylic acid methyl ester and acrylic acid amide and the corresponding methacrylic acid compounds, maleic acid, maleic acid methyl ester, maleic acid dimethyl and diethyl ester, halogenated vinyl compounds, such as, for example, vinyl chloride, vinyl fluoride, vinylidene chloride or vinylidene fluoride, vinyl esters and vinyl ethers, such as, for example, vinyl acetate, methyl vinyl ether and butyl vinyl ether.
- Other suitable compounds are, for example, allyl bromide, allyl chloride and allyl cyanide.
- the polymerisation is normally initiated by one of the customary initiators of free-radical polymerisation.
- the latter include thermal initiators, such as azo compounds, for example ⁇ , ⁇ '-azoisobutyronitrile (AIBN), or peroxides, for example benzoyl peroxide, or redox initiator systems, such as a mixture of iron(III) acetyl acetonate, benzoin and benzoyl peroxide, or photochemical free-radical formers, such as benzoin or benzildimethyl ketal.
- thermal initiators such as azo compounds, for example ⁇ , ⁇ '-azoisobutyronitrile (AIBN)
- peroxides for example benzoyl peroxide
- redox initiator systems such as a mixture of iron(III) acetyl acetonate, benzoin and benzoyl peroxide
- photochemical free-radical formers such as benzoin or benzildimethyl ketal.
- the polymerisation is preferably carried out in solution.
- the reaction temperature generally varies within a range of from 10° to 200° C., preferably from 40° to 150° C., most preferably from 40° to 100° C.
- solvents that may be present must be inert under the reaction conditions.
- Suitable solvents are inter alia aromatic hydrocarbons, chlorinated hydrocarbons, ketones and ethers. Examples of these are: benzene, toluene, xylenes, ethylbenzene, isopropylbenzene, ethylene chloride, propylene chloride, methylene chloride, chloroform, methyl ethyl ketone, acetone, cyclohexanone, diethyl ether and tetrahydrofuran.
- copolymers according to the invention are suitable for the preparation of highly sensitive negative resist compositions that can be developed in an aqueous-alkaline medium.
- the invention also relates, therefore, to photosensitive compositions comprising
- Suitable compounds ii) that form an acid under actinic radiation are especially onium salts, such as diazonium, sulfonium, sulfoxonium and iodonium salts.
- onium salts such as diazonium, sulfonium, sulfoxonium and iodonium salts.
- Preferred are sulfonium salts of formula VIII
- Ar 1 is phenyl, naphthyl or phenyl--COCH 2 -- each unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, --OH and/or by nitro
- Z 1 is C 1 -C 6 alkyl or C 3 -C 7 cycloalkyl and Z 2 is tetrahydrothienyl, tetrahydrofuryl or hexahydropyryl
- q is 0, 1, 2 or 3
- r is 0, 1 or 2 and s is 0 or 1, the sum of q+r+s being 3
- X 1 .sup. ⁇ is chloride, bromide or iodide anion, BF 4 .sup. ⁇ , PF 6 .sup. ⁇ , AsF 6 .sup. ⁇ , SbF 6 .sup. ⁇ , FSO.sup. ⁇ or the anion of an organic sulfonic or carb
- Phenyl, naphthyl and phenacyl groups Ar 1 are preferably mono-substituted, especially by Cl, Br, methyl, methoxy, --OH or nitro. Most preferably, these radicals are unsubstituted.
- Z 1 is preferably C 1 -C 4 alkyl, especially methyl or ethyl.
- q is 2 or 3
- r is 1 or zero and s is zero, and, especially, q is 3 and r and s are zero.
- Ar 1 is unsubstituted phenyl and q is 3.
- X 1 .sup. ⁇ is the anion of an organic sulfonic or carboxylic acid
- it may be an anion of an aliphatic, cycloaliphatic, carbocyclic-aromatic, heterocyclic-aromatic or araliphatic sulfonic or carboxylic acid.
- These anions may be substituted or unsubstituted.
- Preferred are only weakly nucleophilic sulfonic and carboxylic acids, for example partially fluorinated or perfluorinated derivatives or derivatives that are substituted in a position adjacent to the respective acid group.
- substituents are halogen, such as chlorine and especially fluorine, alkyl, such as methyl, ethyl or n-propyl, or alkoxy, such as methoxy, ethoxy or n-propoxy.
- aliphatic sulfonic acids are methane-, ethane-, n-propane-, n-butane- and n-hexane-sulfonic acid or the corresponding partially fluorinated or perfluorinated derivatives thereof.
- aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, 2-ethylhexylcarboxylic acid and fatty acids, such as lauric acid, myristic acid or stearic acid, and the partially fluorinated or perfluorinated derivatives of those acids.
- cycloaliphatic sulfonic and carboxylic acids are cyclohexanesulfonic acid, cyclohexanecarboxylic acid, camphor-10-sulfonic acid or the partially fluorinated or perfluorinated derivatives thereof.
- carbocyclic-aromatic sulfonic acids examples include benzene-, toluene-, ethylbenzene-, isopropylbenzene-, dodecylbenzene- or dimethylbenzene-sulfonic acid, 2,4,6-triisopropylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, naphthalenemono-, -di- or -tri-sulfonic acids, and the corresponding alkylated or partially fluorinated or perfluorinated derivatives of those sulfonic acids.
- heterocyclic-aromatic sulfonic acids are pyridine-, thiophene- or pyrrole-sulfonic acid and the corresponding partially fluorinated or perfluorinated derivatives of those acids.
- araliphatic sulfonic acids are benzylsulfonic acid, ⁇ -methylbenzylsulfonic acid and the corresponding partially fluorinated or perfluorinated derivatives of those compounds.
- carbocyclic-aromatic carboxylic acids are benzoic acid, toluene-, ethylbenzene-, isopropylbenzene- or dimethylbenzene-carboxylic acid, naphthalenecarboxylic acid or anthracenecarboxylic acid and the corresponding partially fluorinated or perfluorinated derivatives of those compounds.
- heterocyclic-aromatic carboxylic acids are pyridine-, thiophene-or pyrrole-carboxylic acid and the corresponding partially fluorinated or perfluorinated derivatives of those compounds.
- araliphatic carboxylic acids are benzylcarboxylic acid, ⁇ -methylbenzylcarboxylic acid and cinnamic acid, and the corresponding partially fluorinated or perfluorinated derivatives of those compounds.
- X 1 .sup. ⁇ is preferably the mono-valent anion of an organic sulfonic acid, especially a partially fluorinated or perfluorinated sulfonic acid. These anions are distinguished by being especially weakly nucleophilic.
- Suitable sulfonium salts of formula VIII are triphenylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium iodide, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride, phenacyltetrahydrothiophenium chloride, 4-nitrophenacyltetrahydrothiophenium chloride and 4-hydroxy-2-methylphenylhexahydrothiopyrylium chloride. Triphenylsulfonium trifluoromethanesulfonate is especially preferred.
- Ar 2 and Ar 3 each independently of the other are phenyl or naphthyl each unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen and/or by nitro, or Ar 2 and Ar 3 together are a group of formula X ##STR14## wherein Z 3 is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or nitro and Y is a direct bond, --O--, --CH 2 -- or --CO--- and X 2 .sup. ⁇ is a chloride, bromide or iodide anion. Iodonium salts of formula IX are described, for example, in GB-A 1 539 192.
- Also suitable as compounds ii) are substances of formulae XI to XVII that produce sulfonic acid under actinic radiation ##STR15## wherein t is 1 or 2, preferably 1, Z 4 is phenyl or naphthyl each unsubstituted or substituted by from 1 to 3 --Cl, --Br, --CN, --NO 2 , C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, C 1 -C 4 alkylamino, C 2 -C 4 dialkylamino or benzoyl substituents, especially unsubstituted phenyl or phenyl mono-substituted by --Cl, methyl or by methoxy, Z 5 is hydrogen or C 1 -C 4 alkyl and Z 6 is hydrogen, C 1 -C 4 alkyl or phenyl, or Z 5 and Z 6 together with the linking carbon atom form
- Alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbamoyl and alkylene groups according to the definition may be straight-chain or branched, but are preferably straight-chain.
- Halogen is especially --Cl or --Br.
- Suitable compounds ii) are o-nitrobenzaldehydes that are rearranged under actinic radiation to form o-nitrosobenzoic acids, such as 1-nitrobenzaldehyde and 2,6-dinitrobenzaldehyde; ⁇ -haloacylphenones, such as ⁇ , ⁇ , ⁇ -trichloroacetophenone and p-tert-butyl- ⁇ , ⁇ , ⁇ -trichloroacetophenone, and sulfonic acid esters of o-hydroxyacylphenones, such as 2-hydroxybenzophenone methanesulfonate and 2,4-hydroxybenzophenone bis(methanesulfonate).
- o-nitrobenzaldehydes that are rearranged under actinic radiation to form o-nitrosobenzoic acids, such as 1-nitrobenzaldehyde and 2,6-dinitrobenzaldehyde
- ⁇ -haloacylphenones such as ⁇ , ⁇ , ⁇ -
- Examples of such compounds are hexafluorotetrabromobisphenol A, 1,1,1-tris(3,5-dibromo-4-hydroxyphenyl)ethane and N-(2,4,6-tribromophenyl)-N'-(p-toluenesulfonyl)urea.
- Especially preferred anions X 1 .sup. ⁇ are CF 3 SO 3 .sup. ⁇ , C 2 F 5 SO 3 .sup. ⁇ , n-C 3 F 7 SO 3 .sup. ⁇ , C 4 F 9 SO 3 .sup. ⁇ , n-C 6 F 13 SO 3 .sup. ⁇ , n-C 8 F 17 SO 3 .sup. ⁇ and C 6 F 5 SO 3 .sup. ⁇ .
- the compounds ii) are advantageously employed in an amount of from 0.1 to 20% by weight, especially from 1 to 10% by weight and most especially from 1 to 6% by weight, based on the weight of the copolymer.
- compositions according to the invention may comprise other customary additives, such as e.g. binders, stabilisers, pigments, dyes, fillers, adhesion promoters, leveling agents, wetting agents and plasticisers.
- binders e.g. binders, stabilisers, pigments, dyes, fillers, adhesion promoters, leveling agents, wetting agents and plasticisers.
- suitable solvents e.g. binders, stabilisers, pigments, dyes, fillers, adhesion promoters, leveling agents, wetting agents and plasticisers.
- the binder is selected in accordance with the field of application and the properties required for that field of application.
- Suitable binders are, for example, novolaks derived from an aldehyde, preferably formaldehyde, acetaldehyde or furfuraldehyde, but especially formaldehyde, and a phenol.
- the phenolic component of these binders is preferably phenol itself or, alternatively, halogenated phenol, for example phenol substituted by one or two chlorine atoms, preferably p-chlorophenol, or it is a phenol substituted by one or two C 1 -C 9 alkyl groups, for example o-, m-or p-cresol, a xylenol, p-tert-butylphenol or p-nonylphenol.
- the phenol component of the preferred novolaks may, however, also be p-phenylphenol, resorcinol, bis(4-hydroxyphenyl)methane or 2,2-bis(4-hydroxyphenyl)propane.
- binders are, for example, copolymers of maleic anhydride with styrene, vinyl ethers or 1-alkenes.
- Homo- or co-polymeric acrylates and methacrylates for example copolymers of methyl methacrylate/ethyl acrylate/methacrylic acid, poly(methacrylic acid alkyl esters) or poly(acrylic acid alkyl esters) containing, for example, from 1 to 20 carbon atoms in the alkyl radical, can also be used as binders.
- binder there is preferably used as binder an alkali-soluble substance, for example a novolak (which may be modified as described above), poly(4-hydroxystyrene) or poly(4-hydroxy-3,5-dimethylstyrene), copolymers of maleic anhydride with styrene, vinyl ethers or 1-alkenes, and copolymers of acrylic or methacrylic acid esters with ethylenically unsaturated acids, for example methacrylic acid or acrylic acid.
- a novolak which may be modified as described above
- copolymers of maleic anhydride with styrene vinyl ethers or 1-alkenes
- acrylic or methacrylic acid esters with ethylenically unsaturated acids for example methacrylic acid or acrylic acid.
- the photosensitive compositions according to the invention are eminently suitable as coating compositions for substrates of all kinds, for example wood, textiles, paper, ceramics, glass, plastics, such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and metals, such as Al, Cu, Ni, Fe, Zn, Mg or Co, and GaAs, Si or SiO 2 , to which an image is to be applied by image-wise exposure.
- substrates of all kinds for example wood, textiles, paper, ceramics, glass, plastics, such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and metals, such as Al, Cu, Ni, Fe, Zn, Mg or Co, and GaAs, Si or SiO 2 , to which an image is to be applied by image-wise exposure.
- the choice of solvent and the concentration are governed primarily by the nature of the composition and the coating method.
- the solvent should be inert, i.e. it should not undergo chemical reaction with the components, and it should be capable of being removed again during drying after the coating operation.
- Suitable solvents are, for example, ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate.
- the solution is uniformly applied to a substrate by known coating methods, for example by spin-coating, dip-coating, doctor coating, curtain coating methods, brushing, spraying, especially by electrostatic spraying and reverse roll coating. It is also possible to apply the photosensitive layer to a temporary, flexible carrier and then to coat the final substrate, for example a copper-clad circuit board, by layer transfer via lamination.
- the quantity applied (coating thickness) and the type of substrate (coating carrier) depend upon the desired field of application.
- the coating thickness range generally encompasses values of approximately from 0.1 ⁇ m to more than 10 ⁇ m.
- coating thicknesses for photographic materials and offset printing blocks are normally approximately from 0.5 ⁇ m to 10 ⁇ m and, for printed circuits, from 0.4 to approximately 2 ⁇ m.
- compositions according to the invention it is possible to produce high-resolution relief structures of negative tonality. Owing to the high sensitivity and the high optical transparency or, in other words, the low optical absorption in the UV range around 250 nm, they are especially suitable for microlithography applications, especially deep UV microlithography. Owing to those properties, very steep wall profiles can be obtained and the resolution of submicron structures (down to 0.5 ⁇ m) can be achieved. Such submicron structures cannot be produced, for example, with corresponding compositions containing an acetoxymethyl function in the copolymer molecule.
- the solvent is generally removed by drying, producing a layer of photoresist on the carrier.
- image-wise exposure includes exposure through a photomask containing a predetermined pattern, for example a diapositive, exposure by a laser beam which is moved over the surface of the coated substrate, for example by computer control to produce an image, and irradiation with computer-controlled electron beams.
- the photosensitivity of the compositions according to the invention generally extends from the UV region (approximately 200 nm) to approximately 600 nm and thus spans a very broad range. Therefore, a large number of very different light sources are employed. Both point sources and arrays of reflector lamps are suitable. Examples are carbon arc lamps, xenon arc lamps, mercury vapour lamps, which may be doped with metal halides (metal halide lamps), fluorescent lamps, argon glow lamps, electronic flash lamps, photographic flood lamps, electron beams and X-rays produced by means of synchrotrons or laser plasma.
- the distance between the lamp and the image material according to the invention may vary, for example between 2 cm and 150 cm, according to the utility and the type and intensity of the lamp.
- Laser light sources for example excimer lasers, such as krypton fluoride lasers, for exposure at 248 nm are especially suitable.
- the high sensitivity of the materials according to the invention is very advantageous in this connection.
- the unexposed areas of the photoresist are removed in a manner known per se using a developer.
- compositions according to the invention can be developed in an aqueous-alkaline medium.
- Suitable aqueous-alkaline developer solutions are, especially, aqueous solutions of tetraalkylammonium hydroxides or of alkali metal silicates, phosphates, hydroxides and carbonates.
- relatively small amounts of wetting agents and/or organic solvents may additionally be added to those solutions.
- Typical organic solvents that may be added in small amounts to the developer fluids are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.
- compositions according to the invention are especially suitable for the manufacture of printing plates, printed circuits and integrated circuits.
- the resulting oil can be purified by column chromatography (stationary phase silica gel, mobile phase hexane/ether 5/4) to yield 2.54 g (10.8 mmol, 21% of the theoretical yield) of the desired substance in the form of a clear oil.
- GPC polystyrene calibration
- the phenol in the structural elements consisting of 4-tetrahydropyran-2-yloxystyrene is freed by stirring for 60 minutes at room temperature in tetrahydrofuran under an inert gas atmosphere in the presence of a catalytic amount of acetic acid.
- GPC polystyrene calibration
- a resist mixture is prepared by dissolving 90 parts by weight of the copolymer according to Example 7 and 10 parts by weight of triphenylsulfonium trifluoromethanesulfonate in 350 parts by weight of cyclopentanone. This mixture is spin-coated onto a silicon wafer and dried at 120° C. for 2 minutes to produce a resist film having a coating thickness of 1.0 ⁇ m which is subsequently exposed image-wise through a quartz mask.
- the light source used is a mercury vapour lamp which remains switched on for 3 seconds. After exposure, heating is carried out at 90° C. for 3 minutes and then developing is carried out in a solution of 15% by weight tetramethylammonium hydroxide in water. The exposed areas of the film are retained in the form of relief structures of the original thickness while the unexposed areas are dissolved.
- the resulting resist material permits the resolution of submicron structures.
- a resist solution is prepared by dissolving 96 parts by weight of the copolymer according to Example 8 and 5 parts by weight of triphenylsulfonium trifluoromethanesulfonate in 250 parts by weight of cyclohexanone.
- the solution is spin-coated onto a silicon wafer and is then dried at 120° C. for 2 minutes to produce a resist film of 1.1 ⁇ m thickness.
- the optical density of that film, measured on a quartz wafer has at 248 nm a value of 0.32.
- the wafer coated with the resist film is then contact-exposed through a quartz mask with an interference narrow band filter at 254 nm and at a dose of 20 mJ/cm 2 and is subsequently heated at 120° C. for 1 minute.
- the exposed areas of the film remain behind in the form of relief structures of the original thickness while the unexposed areas are dissolved.
- the resulting resist material is capable of reproducing, at a contrast value ⁇ of 3.0, structures down to 0.5 micrometers l/s (lines and spaces) true to line and without swelling.
- the resist solution obtained in accordance with Example 11 is applied by brushing to a copper-clad circuit board and drying is carried out at 100° C. for 15 minutes in a hot oven to produce resist films having a coating thickness of 15 ⁇ m. Exposure is then carried out for 15 seconds through a mask using a mercury vapour lamp, and the board is then kept at 120° C. for 2 minutes. Developing is subsequently carried out in a 2.38% by weight solution of tetramethylammonium hydroxide in water for 1 minute, the exposed areas of the resist film remaining behind and the unexposed areas being dissolved.
Abstract
Description
(Ar.sub.1).sub.q (Z.sub.1).sub.r (Z.sub.2).sub.s S.sup.⊕ X.sub.1.sup.⊖ (VIII),
[Ar.sub.2 --I.sup.⊕ --Ar.sub.3 ]X.sub.2.sup.⊖ (IX)
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH624/91 | 1991-03-01 | ||
CH62491 | 1991-03-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
US5274060A true US5274060A (en) | 1993-12-28 |
Family
ID=4191344
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/843,798 Expired - Lifetime US5274060A (en) | 1991-03-01 | 1992-02-27 | Copolymers crosslinkable by acid catalysis |
Country Status (6)
Country | Link |
---|---|
US (1) | US5274060A (en) |
EP (1) | EP0502819A1 (en) |
JP (1) | JPH07179522A (en) |
KR (1) | KR920018101A (en) |
BR (1) | BR9200710A (en) |
CA (1) | CA2062096A1 (en) |
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US5807947A (en) * | 1988-10-21 | 1998-09-15 | Clariant Finance (Bvi) Limited | Copolymers 4-hydroxystyrene and alkyl substituted-4-hydroxystyrene |
US6166161A (en) * | 1996-06-24 | 2000-12-26 | The Dow Chemical Company | Incorporation of functionalized comonomers in polyolefins |
US20050228191A1 (en) * | 2004-03-26 | 2005-10-13 | Keith Kunitsky | Method for preparing hydroxystyrenes and acetylated derivatives thereof |
US20070213569A1 (en) * | 2006-03-07 | 2007-09-13 | Shuey Steven W | Processes for conversion of tyrosine to p-hydroxystyrene and p-acetoxystyrene |
US20070263488A1 (en) * | 2006-05-10 | 2007-11-15 | Schlumberger Technology Corporation | Wellbore telemetry and noise cancellation systems and method for the same |
US20080167433A1 (en) * | 2007-01-04 | 2008-07-10 | Keith Kunitsky | Method for preparing glycidyloxystyrene monomers and polymers thereof |
US7705176B2 (en) | 2005-10-27 | 2010-04-27 | Polnox Corporation | Macromolecular antioxidants based on sterically hindered phenols and phosphites |
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KR20220044564A (en) | 2019-08-09 | 2022-04-08 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Compound, polymer, composition, composition for film formation, pattern formation method, insulating film formation method and compound production method, and method for producing iodine-containing vinyl polymer and acetylated derivatives thereof |
US11578285B2 (en) | 2017-03-01 | 2023-02-14 | Polnox Corporation | Macromolecular corrosion (McIn) inhibitors: structures, methods of making and using the same |
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KR20220044564A (en) | 2019-08-09 | 2022-04-08 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Compound, polymer, composition, composition for film formation, pattern formation method, insulating film formation method and compound production method, and method for producing iodine-containing vinyl polymer and acetylated derivatives thereof |
Also Published As
Publication number | Publication date |
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BR9200710A (en) | 1992-11-10 |
EP0502819A1 (en) | 1992-09-09 |
KR920018101A (en) | 1992-10-21 |
CA2062096A1 (en) | 1992-09-02 |
JPH07179522A (en) | 1995-07-18 |
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